Basic condensation products containing nitrogen



United States Patent BASIC CONDENSATION PRODUCTS CONTAINING NITROGEN No Drawing. Application December 4, 1952 Serial No. 324,119

Claims priority, application Switzerland December 7, 1951 3 Claims. (Cl. 260-459) The present invention relates to basic condensation products containing nitrogen. I More. particularly, the invention is concerned with .the embodiment. of condensation products of the indicated type which, because of the properties imparted thereto. by the characteristic structure thereof, as hereinafterset forth,.are especially suitable as dyeing. auxiliaries, inttlie dyeing of textiles and the like. While the dyeing auxiliary art is a highly developed one, there is still room for additional products and especially those which, like the products of the present invention, are easily watersoluble and can be used in neutral, acid or alkaline baths.

The nitrogenous condensation products of the present invention are prepared by reacting an ether which corresponds totheformula O" O H halogen with a polyamine of the formula Ra HN A-N ]A-N R1 I la "-1 \RA wherein each of.R ,,R R and R stands for a hydrogen atom, an alkyl or aralkyl orhydroxyalkyl group or a polyglycoletherradical, A standsfor an alkylen'e group containing 2 to 4 carbon atoms, and n is a whole num= her, and wherein, in the event n is one, less than all of R R R and R stand for hydrogen atoms.

appropriate cases, the product obtained as a. result of .the: reaction described in the preceding paragraph may be subjected to the action of an alkylating agent, whereby a quaternary ammonium compound results which, for the indicated purpose (dyeing assistant), is equally as good as the free base, and in some cases may give rise to additional desirable properties (as for example, germicidal activity) due to the presence of the onium radical.

In carrying out the present invention, the following compounds are particularly suitable as starting materials:

a)1 Ethers: octyloxypropenoxide, dodecyloxypropen oxide, hexadecyloxypropenoxide, octadecyloxypropenox ide, octadecenyloxypropenoxide, alkylphenoxypropenoxides, compounds of the formula R-(O CHi) ,.0-CH2CH CH wherein n isaiwliolenumber and R is any desired hydrocarbon chain containing 8-24 carbon atoms, and also the halogenhydrins. corresponding to the afore-enumerated epoxides.

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The halogenhydrins corresponding to the above named epoxides may be prepared from the corresponding alcohols by reacting them by known methods in the presence of acidic catalysts with glycerolepihalogenides such as epichlorhydrin and the above named epoxides: by treating the corresponding halogenhydrins also by known methods with alkaline agents which are capable of splitting ofi halogenohydric acids.

(b) Polyamines: diethylenetriamine, dipropylenetriamine, poly-ethyleneand/or polypropylene-polyamines, methylamino-ethylamine, 3-isopropylarnino-propylamine- 1, and 3,3-dimethylamino-propylamine-l, etc.

The condensation products obtained from the ethers and amines according to the invention can, if desired and if. they contain alkylatable nitrogen atoms, be alkylated or peralkylated (quaternized) by treatment with alkylating agents such for example as ethylene oxide, dimethyl sulfate, diethyl sulfate, chloracetic acid, chloroxypropane-sulfonic acid; benzyl chloride, etc.

The reaction of the aforedescribed components is preferably carried out'at elevated temperature, e. g. between 40 and 160 C. The reaction products are oily to viscous liquid products, which are readily soluble in water and which correspond, in the case of the nonalkylated products, to the formula RO GHQ-('1 H-C H2[ III-A I|\ Ra OH R1 1| R2 and, in the case of the alkylated products, to the formula V i R Anion R" Anion RO-CH-CH-CH2[ \IITZA' l|I Rs R1 1| R2 wherein R, R R R R A and n have the previouslyindi'cated significances, and wherein R and R" represent the groups introduced by the alkylation.

As hereinbefore set forth, the products of the invention areprimarily intended to be'usedas dyeing assistants, and in this connection they may be employed as such or in admixture with suitable and conventional additional substances;

Theproducts which maybe obtained asdescribedebove show excellent levelling, penetrating and stripping action for substantive, acid, basic, chrome and vat dyestuffs, when applied in suitable dissolved or emulsified state.

The following examples illustrate the invention by means of representative exemplary embodiments thereof. In thesaid examples, the temperatures are expressed in degrees Centigrade.

Example 1 1 mol of n-octyloxypropenoxide CgHnOCHr-CH-Cfig O is admixed with 2 mols of die'thylenetriamine and the mixture heated to 100l20, whereupon reaction ensues. Upon completion of the reaction, any unrea'cted diethyl enetriamine'which remains in the reaction mixture is distilled off under reduced pressure, and the/residue reacted with 8 rnols of ethylene oxide at 100 and thereafter with 3 mols of dimethyl sulfate at 50-60". Upon completion ofthereaction, heating is continued for two more hours at 85, whereupon all the dimethyl sulfate' will: be consumed. There is obtained abrownish, viscous, readily water-soluble mass.

Example 2 1 mol' of n-dodecyloxypropenoxide (112E250 CHPC HC Hg 2,817,675 Y is reacted, after the manner described in Example 1, with grams) of water. Thereupon 4 mols of caustic sod 2 mols of diethylenetriamine, and then with 8.5 mols of (NaOI-I) in the form of an aqueous solution of 38% by ethylene oxide and 3 mols of dimethyl sulfate. There is weight strength are also added dropwise, while stirring obtained a brownish, jelly-like, readily water-soluble mass. thoroughly, at 6070. Upon suitable drying, for example 5 in an atomizer, there is obtained a light powder which Example 3 apart from sodium chloride, contains the compound of 1 mol of oleyloxypropenoxide the formula CiaHa5OCH2-CH-CHz CH COONa CHOOONB. \0/ 018E350 CHr-(|)H-C Hz-N-CzHr-N-CglL-N is reacted after the manner described in Example 1, first 0H CmQQQNa gmooom with 2 mols of diethylenetriamine then with 8.5 mols of ethylene oxide, and finally with 3 mols of dimethyl sulas the p rmclp a1 mgredlent fate. The resultant product dissolves easily in water. It xample 8 corresponds to the formula 1 mol of oleyloxypropenoxide is added dropwise and- The corresponding non-alkylated product has the formula with stirring, at 100, to 2 mols of ethylenediamine hydrate, and the mixture then further stirred at 120 for 4 hours. Excess amine and water are thereupon removed ClaHli-oCH2OH-CH2 N CH N CHN by distillation under reduced pressure, the residue being 0H (Z)m (Zn-H obtained in the form of a thickly viscous, brownish oil In these formulae, each Z represents an ethenoxy group which consists Predominantly 0f the compound of the and each m stands for a positive integer, the total number formula of Z groups being from 8 to 01811350 CH2CHCHr-NHOzHr-NH;

The nonmethylated product is an excellent levelling 6 2223i f o i vzi d yss i fi s i muhylated one a good levenmg If one mol of this product is reacted with 5 mols ol Example ethylene oxide at 100 C., there is obtained a brownish, viscous oil which is readily soluble in water and which 1 mol of iso-octylphenoxypropenoxide is reacted, after is a good levelling agent for acid dyestuffs. the manner described in Example 1, at 100-120 with 2 Emmple 9 mols of diethylene triamine and, after removal of excess of the latter, ethylene oxide is introduced into the resultant To 1 mol of 3-1s0propylamino-propylamine-1, there is compound of the formula 40 gradually added, while stirring at l00, 1 mol of oleyloxypropenoxide, after which the mixture is heated for 4 more hours at 120", with further stirring. There is ob- OQHWO f tained a brownish, viscous oil, consisting principally of 0 the compound of the formula at- 100 until 7 mols of ethylene oxide have been taken CH.

up. The resultant product is then reacted at 60-80 with 3 mols of dimethyl sulfate. There is thus obtained a cl'moCHTCHTOHPNIFCHOHCHPNEFCH t H CH bl'OWfllSi], readily water soluble, elly h e pas e Example 10 Example 5 Ethylene oxide is introduced, with stirring, into 1 mol The procedure according to Example 3 is repeated, ex- 0f e pound prepared according to Example 9, until cept that instead of 3 mols of dimethyl sulfate, 1.5 mols 2 111015 0f ethylene oxlde are taken P- of benzyl chloride are used for the alkylation. A product Example 11 similar to that of Example 3 is obtained.

The unalkylated product is a brownish, viscous, read1ly water-soluble oil.

At a temperature of 100, 1 mol of oleyloxypropenoxide is slowly added to 1 mol of dimethylamino-propylamine-l, after which the mixture is heated to 120-130 for 4 v hours. A brownish product is obtained, the major pot.- 1 mol of the compound tion of which corresponds to the formula is reacted at 100-120 with 1 mol of diethylenetriamine. H

The product is a brownish viscous oil which is readily Example 12 soluble in water.

In lieu of 1 mol of diethylenetriamine, the aforesaid epoxide (1 mol) may also be reacted with any other suitable polyalkylenepolyamine, a similar product being obtained in each case.

Example 6 One mol of n-octadecenyloxypropenoxide is admixed with 1.2 mols of diethylenetriamine and the mixture heated to 100120 C., whereupon reaction ensues. After completion of the reaction the temperature is lowered to 50 C., whereupon one mol of dimethylsulfate and 1.2 mols of 30% aqueous sodium-hydroxide solution is 1 mol of oleyloxypropenoxide is stirred for 4 hours with added and the temperature kept at 50 C. till reaction is an excess of diethylenetriamine at 100420", unreacted complete. The methylated reaction product thus obdiethylenetriamine being thereupon distilled ofi under retained is heated to 120 C. and reacted with 4.2 mols of Example 7 duced pressure. The residue is then added dropwise with ethylene oxide. There is obtained a brownish viscous stirring at 40-50 to a solut1on of 4 mols (378 grams) of readily water-soluble oil. Used in small concentrationsin monochloracettc acid in the hke amount by weight (378 the acid dye bath it shows an excellent levelling action L 6 r Example 13 with 1.1 mols of tetraethylenepentamirre: .Tfie' resulting One mol of n-octadecenyloxypropenoxide is reacted in product chiefly consists of a compound of the probable a suitable closed vessel at a temperature of 100 to 120 formula:

GET-CH;

CH3-C OHi-O-CH GiEKOH)CH:NH-OzH4-NH--CaH -NHC2H -NH-CgH -NH;

CH2-C r l with 1.2 mols of diethylenetriamine. After completion of It is a brownish oil, which is readily soluble in water and the reaction, 7.0 mols of ethyleneoxide are introducedinto which, even in smallquantities, shows a good levelling the resultant compound at a temperature of 120. The 15 action in acid dye baths.

temperature is now lowered to 50 C. and the oxyethyl- E l 19 ated compound reacted with two mols of epichlorhydrin. xamp e The resulting product, which consists of a brownish One mol of XylenyloXypropenoXide is reacted at a tem viscous readily Water-soluble mass, shows an excellent Peratllre of with 11 111018 of diethylenetriamille,

levelling ti i id dye b th even h d i 20 by stirring the two reactants for four hours at said temsm ll once ti n perature. The resulting compound is a viscous brownish Example 14 oil, which essential ingredient probably corresponds to At a temperature of 100-120 one mol of tetraethylthe following formula:

enepentamine is reacted with two mols of n-octadecenyl- 0113 oxypropenoxide and after completion of the reaction fur- -OCH2CH(0H)-CHHNfi-CQHFNH-CzHa-NH: ther reacted at a temperature of 120 C. with a 4.5 mols CH3 of ethyleneoxide. The resulting reaction product is a brownish, viscous oil readily soluble in water, which shows A compound with Similar Properties may {be obtained if a polyamine boiling above 206 at 12 mm. mercury a good levenmg actlon m and dyg baths' gauge is employed instead of diethylenetriamine.

Example 15 Such a compound shows, when emulsified with an One mol of n-octadecenyloxypropenoxide is reacted at oleylpolyglycolethel containing 9 t0 20 H1018 of ethylenea temperature of 100-120 C. with 1.2 mols of diethy oxide per mol oleylalcohol, an excellent levelling action enetriamine. The resulting product is further reacted at acld y a temperature of 120 with 0.5 mol of ethyleneoxide. Example 20 After completion of the reaction, the temperature is low o mol f the epoxide of the formula ered to -50", whereupon one mol of finely divided sodium hydroxide and one mol of the sodium salt of chloro- 57 acetic acid is added. After stirring at 50 for three hours 40 0 the reaction is complete. The resulting compound is a prepared from dodecylmetcaptan; two mols of ethylenebrownish, Sticky Paste Which is readily bl in Water oxide and one mol of epichlorhydrin is reacted at a temand which shows, even in small proportions, an excellent pefatllre of 100-120 with 1.2 mols of diethylenetrilevelling action in acid dye baths. amine by stirring the reactants for four hours at said Example 16 temperature. The resulting compound is a viscous, brownish oil which 18 soluble in water and which shows One mol of diamylphenoxypropenoxide 1s first reacted good levelling action f acid d t fl at a temperature of 1001 h 111015 of Q Y Having thus disclosed the invention, what is claimed is: enetriamlne and then, at the Same temperature, Wlth 7 1. A basic, nitrogenous condensation product selected mols of ethyleneoxide- The temperature is now f' from the group consisting of the products of the formulae to 50 and the oxyethylated compound reacted at the said temperature with 3 mols of dimethylsulfate. After com- (ZMTH pletion of the reaction there is obtained a brownish, C18335-4)CHPCHCH2-NC2H4NO2H4N water-soluble, very viscous oil. This compound shows, OH (Z)M H (Z)M H (Z)m H even in small quantities, a very strong stripping action on vat dyes. and

Example 17 whereircij eafch Z stands for an ethetrlieoxy group Iand ezrcg m stan s or a ositlve in e er, t e tota num er 0 At a temperature of 100-120 one mol of n-octadecengr cups being g 8 to 9. g

yloxypropenoxld? 1s first brolight mm reacnon with 1 mol 2. A basic, nitrogenous condensation product of the of 3-dimethylam1nopropylarnme and then, for five hours, farmula at a temperature of 85, with two mols of glycerolmonochlorhydrin. The resulting compound is a water- (Z)m H soluble, brownish, viscous oil which, even in smalhquan- 70 Gumbo tities, greatly improves the stripping effect of stripping baths for vat dyed cellulosic materials. 0H )H (Zn-H Example 18 wherein each Z stands for an ethenoxy group and each m 1 mol of methylcyclohexyloxypropenoxide is reacted stands for a positive integer, the total number of Z groups for four hours, by stirring, at a temperature of -120 being from 8 to 9.

2, 75 wherein each Z stands for an ethenoxy group and each m stands for a positive integer, the total number of Z groups being from 8 to 9.

3. A basic, nitrogenous condensation product of the formula References Cited in the file of this patent UNITED STATES PATENTS 2,334,517 Tucker Nov. 16, 1943 2,523,177 Yowell et a1 Sept. 19, 1950 2,527,963 Rieveschl Oct. 31, 1950 

1. BASE NITROGENOUS CONDENSATION PRODUCT SELECTED FROM THE GROUP CONSISTING OF THE PRODUCTS OF THE FORMULAE 